公开(公告)号：US09738685B2

公开(公告)日：2017-08-22

申请号：US15017049

申请日：2016-02-05

Applicant: YEDA RESEARCH AND DEVELOPMENT CO. LTD.

Inventor： David Milstein ,  Chidambaram Gunanathan ,  Yehoshua Ben-David ,  Ekambaram Balaraman ,  Boopathy Gnanaprakasam ,  Jing Zhang

IPC: C07K5/12 ,  C07C209/50 ,  C07C213/00 ,  C07C231/00 ,  C07C231/02 ,  C07D307/52 ,  C08L79/02 ,  C07C67/03 ,  C07C45/00 ,  C07C51/235 ,  C07C67/28 ,  C07D241/12 ,  C07D295/185 ,  C07D487/14 ,  C07C29/136 ,  C07C67/39 ,  C07K1/02 ,  C07K1/10

CPC classification number: C07K5/12 ,  C07C29/136 ,  C07C45/002 ,  C07C51/235 ,  C07C67/03 ,  C07C67/28 ,  C07C67/39 ,  C07C209/50 ,  C07C213/00 ,  C07C231/00 ,  C07C231/02 ,  C07C2601/08 ,  C07C2601/14 ,  C07D241/12 ,  C07D295/185 ,  C07D307/52 ,  C07D487/14 ,  C07K1/02 ,  C07K1/10 ,  C08L79/02 ,  Y02P20/52 ,  C07C233/05 ,  C07C235/06 ,  C07C235/10 ,  C07C233/36 ,  C07C211/27 ,  C07C215/28 ,  C08L1/00 ,  C07C69/14 ,  C07C69/24 ,  C07C31/04 ,  C07C31/08 ,  C07C31/10 ,  C07C31/12

Abstract: A process for preparing amides by reacting a primary amine and a primary alcohol in the presence of a Ruthenium complex to generate the amide and molecular hydrogen. Primary amines are directly acylated by equimolar amounts of alcohols to produce amides and molecular hydrogen (the only byproduct) in high yields and high turnover numbers. Also disclosed are processes for hydrogenation of amides to alcohols and amines; hydrogenation of organic carbonates to alcohols; hydrogenation of carbamates or urea derivatives to alcohols and amines; amidation of esters; acylation of alcohols using esters; coupling of alcohols with water and a base to form carboxylic acids; dehydrogenation of beta-amino alcohols to form pyrazines and cyclic dipeptides; and dehydrogenation of secondary alcohols to ketones. These reactions are catalyzed by a Ruthenium complex which is based on a dearomatized PNN-type ligand of formula A1 or precursors thereof of formulae A2 or A3.

公开(公告)号：US08889865B2

公开(公告)日：2014-11-18

申请号：US14297116

申请日：2014-06-05

Applicant: Yeda Research and Development Co. Ltd.

Inventor： David Milstein ,  Chidambaram Gunanathan

IPC: C07F15/00 ,  B01J21/02 ,  C07F5/02 ,  C07C209/16 ,  C07D307/52 ,  B01J31/14 ,  C07D213/38 ,  C07D305/06

CPC classification number: C07C209/16 ,  B01J31/146 ,  C07B43/04 ,  C07C213/02 ,  C07C2601/14 ,  C07D213/38 ,  C07D305/06 ,  C07D307/52 ,  C07F9/60 ,  C07F9/64 ,  C07F15/0046 ,  C07C211/07 ,  C07C211/17 ,  C07C211/27 ,  C07C217/08 ,  C07C217/58

Abstract: The present invention provides novel ruthenium based catalysts, and a process for preparing amines, by reacting a primary alcohol and ammonia in the presence of such catalysts, to generate the amine and water. According to the process of the invention, primary alcohols react directly with ammonia to produce primary amines and water in high yields and high turnover numbers. This reaction is catalyzed by novel ruthenium complexes, which are preferably composed of quinolinyl or acridinyl based pincer ligands.

Abstract translation: 本发明提供新型的钌基催化剂，以及通过在这种催化剂存在下使伯醇和氨反应制备胺的方法，以产生胺和水。 根据本发明的方法，伯醇直接与氨反应，以高产率和高的周转数产生伯胺和水。 该反应由新的钌络合物催化，其优选由喹啉基或吖啶基的钳形配体组成。

公开(公告)号：US20140046065A1

公开(公告)日：2014-02-13

申请号：US14058191

申请日：2013-10-18

Applicant: Yeda Research and Development Co. Ltd.

Inventor： David Milstein ,  Chidambaram Gunanathan

IPC: C07F9/64 ,  C07F9/60

CPC classification number: C07C209/16 ,  B01J31/146 ,  C07B43/04 ,  C07C213/02 ,  C07C2601/14 ,  C07D213/38 ,  C07D305/06 ,  C07D307/52 ,  C07F9/60 ,  C07F9/64 ,  C07F15/0046 ,  C07C211/07 ,  C07C211/17 ,  C07C211/27 ,  C07C217/08 ,  C07C217/58

Abstract: The present invention provides novel ruthenium based catalysts, and a process for preparing amines, by reacting a primary alcohol and ammonia in the presence of such catalysts, to generate the amine and water. According to the process of the invention, primary alcohols react directly with ammonia to produce primary amines and water in high yields and high turnover numbers. This reaction is catalyzed by novel ruthenium complexes, which are preferably composed of quinolinyl or acridinyl based pincer ligands.

公开(公告)号：US08779136B2

公开(公告)日：2014-07-15

申请号：US14058191

申请日：2013-10-18

Applicant: Yeda Research and Development Co. Ltd.

Inventor： David Milstein ,  Chidambaram Gunanathan

IPC: C07F9/28

CPC classification number: C07C209/16 ,  B01J31/146 ,  C07B43/04 ,  C07C213/02 ,  C07C2601/14 ,  C07D213/38 ,  C07D305/06 ,  C07D307/52 ,  C07F9/60 ,  C07F9/64 ,  C07F15/0046 ,  C07C211/07 ,  C07C211/17 ,  C07C211/27 ,  C07C217/08 ,  C07C217/58

Abstract: The present invention provides novel ruthenium based catalysts, and a process for preparing amines, by reacting a primary alcohol and ammonia in the presence of such catalysts, to generate the amine and water. According to the process of the invention, primary alcohols react directly with ammonia to produce primary amines and water in high yields and high turnover numbers. This reaction is catalyzed by novel ruthenium complexes, which are preferably composed of quinolinyl or acridinyl based pincer ligands.

公开(公告)号：US20170107251A1

公开(公告)日：2017-04-20

申请号：US15355082

申请日：2016-11-18

Applicant: YEDA RESEARCH AND DEVELOPMENT CO. LTD.

Inventor： David MILSTEIN ,  Ekambaram Balaraman ,  Chidambaram Gunanathan ,  Boopathy Gnanaprakasam ,  Jing Zhang

IPC: C07K5/12 ,  C07C209/62 ,  C07D305/06 ,  C07D307/44 ,  C07C29/149 ,  C07D295/027 ,  C07D207/06 ,  C07D207/08 ,  C07D211/12 ,  C07C231/10 ,  C07D307/52 ,  C07D295/185 ,  C07C67/00 ,  C07C213/02 ,  C07C51/00 ,  C07D309/30 ,  C07D307/33 ,  C07D307/83 ,  C07C67/297 ,  C07D241/12 ,  C07B41/02 ,  C07B43/04 ,  C07B41/08 ,  C07B41/12 ,  C07B43/06 ,  B01J31/24 ,  C07C41/26

CPC classification number: C07K5/12 ,  B01J31/18 ,  B01J31/189 ,  B01J31/2404 ,  B01J31/2409 ,  B01J31/248 ,  B01J31/2485 ,  B01J2231/40 ,  B01J2231/49 ,  B01J2231/643 ,  B01J2231/763 ,  B01J2531/0244 ,  B01J2531/821 ,  C07B41/02 ,  C07B41/08 ,  C07B41/12 ,  C07B43/04 ,  C07B43/06 ,  C07C29/136 ,  C07C29/149 ,  C07C29/177 ,  C07C41/16 ,  C07C41/26 ,  C07C45/002 ,  C07C45/006 ,  C07C51/00 ,  C07C51/02 ,  C07C51/23 ,  C07C51/295 ,  C07C67/00 ,  C07C67/03 ,  C07C67/297 ,  C07C209/00 ,  C07C209/62 ,  C07C213/00 ,  C07C213/02 ,  C07C231/02 ,  C07C231/10 ,  C07C2601/08 ,  C07C2601/10 ,  C07C2601/14 ,  C07D207/06 ,  C07D207/08 ,  C07D211/12 ,  C07D213/38 ,  C07D241/08 ,  C07D241/12 ,  C07D295/023 ,  C07D295/027 ,  C07D295/185 ,  C07D305/06 ,  C07D307/14 ,  C07D307/33 ,  C07D307/44 ,  C07D307/52 ,  C07D307/83 ,  C07D309/30 ,  C07D487/14 ,  C07F9/58 ,  C07F9/65583 ,  C07F15/0046 ,  C07F15/0053 ,  C07K1/00 ,  C08G69/00 ,  Y02P20/52 ,  C07C233/05 ,  C07C235/06 ,  C07C233/07 ,  C07C235/16 ,  C07C235/14 ,  C07C235/10 ,  C07C211/27 ,  C07C211/07 ,  C07C211/35 ,  C07C211/46 ,  C07C211/10 ,  C07C215/28 ,  C07C217/58 ,  C07C69/14 ,  C07C69/24 ,  C07C31/125 ,  C07C31/12 ,  C07C49/78 ,  C07C49/04 ,  C07C49/10 ,  C07C49/08 ,  C07C49/403 ,  C07C31/205 ,  C07C31/202 ,  C07C31/04 ,  C07C31/08 ,  C07C33/20 ,  C07C33/22 ,  C07C31/1355 ,  C07C31/10 ,  C07C43/13 ,  C07C69/78 ,  C07C69/75 ,  C07C53/124 ,  C07C53/126 ,  C07C59/125 ,  C07C57/32 ,  C07C61/08 ,  C07C57/30 ,  C07C65/21 ,  C07C63/08 ,  C07C63/06

Abstract: The present invention relates to novel Ruthenium complexes and related borohydride complexes, and their use for (1) hydrogenation of amides (including polyamides) to alcohols and amines; (2) preparing amides from alcohols with amines (including preparing polyamides (e.g., polypeptides) by reacting dialcohols and diamines or by polymerization of amino alcohols); (3) hydrogenation of esters to alcohols (including hydrogenation of cyclic esters (lactones), cyclic di-esters (di-lactones) or polyesters); (4) hydrogenation of organic carbonates (including polycarbonates) to alcohols and of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (5) dehydrogenative coupling of alcohols to esters; (6) hydrogenation of secondary alcohols to ketones; (7) amidation of esters (synthesis of amides from esters and amines); (8) acylation of alcohols using esters; (9) coupling of alcohols with water to form carboxylic acids; and (10) dehydrogenation of beta-amino alcohols to form pyrazines. The present invention further relates to novel uses of certain pyridine Ruthenium complexes.

公开(公告)号：US20140288306A1

公开(公告)日：2014-09-25

申请号：US14297116

申请日：2014-06-05

Applicant: YEDA RESEARCH AND DEVELOPMENT CO. LTD.

Inventor： David Milstein ,  Chidambaram Gunanathan

IPC: C07C209/16 ,  B01J31/14 ,  C07D305/06 ,  C07D213/38 ,  C07D307/52

CPC classification number: C07C209/16 ,  B01J31/146 ,  C07B43/04 ,  C07C213/02 ,  C07C2601/14 ,  C07D213/38 ,  C07D305/06 ,  C07D307/52 ,  C07F9/60 ,  C07F9/64 ,  C07F15/0046 ,  C07C211/07 ,  C07C211/17 ,  C07C211/27 ,  C07C217/08 ,  C07C217/58

Abstract: The present invention provides novel ruthenium based catalysts, and a process for preparing amines, by reacting a primary alcohol and ammonia in the presence of such catalysts, to generate the amine and water. According to the process of the invention, primary alcohols react directly with ammonia to produce primary amines and water in high yields and high turnover numbers. This reaction is catalyzed by novel ruthenium complexes, which are preferably composed of quinolinyl or acridinyl based pincer ligands.

Abstract translation: 本发明提供新型的钌基催化剂，以及通过在这种催化剂存在下使伯醇和氨反应制备胺的方法，以产生胺和水。 根据本发明的方法，伯醇直接与氨反应，以高产率和高的周转数产生伯胺和水。 该反应由新的钌络合物催化，其优选由喹啉基或吖啶基的钳形配体组成。